Preface ....................................................... xxi
Foreword to the First Edition ................................. xxv
Mathematical Symbols .........................................xxvii
Abbreviations .............................................. xxxiii
1 Introduction: Subject and Methods ............................ 1
1.1 Objectives .............................................. 1
1.2 Definitions of Chemical Bonding and Transition Metal
Coordination System ..................................... 7
1.3 The Schrddinger Equation ............................... 12
Summary Notes ............................................... 15
References .................................................. 16
2 Atomic States ............................................... 18
2.1 One-Electron States .................................... 18
2.2 Multielectron States: Energy Terms ..................... 35
Summary Notes ............................................... 51
Questions ................................................... 51
Exercises and Problems ...................................... 52
References .................................................. 52
3 Symmetry Ideas and Group-Theoretical Description ............ 54
3.1 Symmetry Transformations and Matrices .................. 54
3.2 Groups of Symmetry Transformations ..................... 60
3.3 Representations of Groups and Matrices of
Representations ........................................ 64
3.4 Classification of Molecular Terms and Vibrations,
Selection Rules, and Wigner-Eckart Theorem ............. 69
3.5 Construction of Symmetrized Molecular Orbitals and
Normal Vibrations ...................................... 74
3.6 The Notion of Double Groups ............................ 81
4 Crystal Field Theory ........................................ 84
4.1 Introduction ........................................... 84
4.2 Splitting of the Energy Levels of One d Electron in
Ligand Fields .......................................... 86
4.3 Several d Electrons .................................... 99
4.4 ƒ-Electron Term Splitting ............................. 115
4.5 Crystal Field Parameters and Extrastabilization
Energy ................................................ 121
4.6 Limits of Applicability of Crystal Field Theory ....... 126
Summary Notes .............................................. 128
Questions .................................................. 129
Exercises and Problems ..................................... 129
References ................................................. 130
5 Method of Molecular Orbitals and Related Approaches ........ 132
5.1 Basic Ideas of the MO LCAO Method ..................... 133
5.2 Charge Distribution and Bonding in the MO LCAO
Method and the Case of Weak Covalency ................. 142
5.3 Methods of Calculation of MO Energies and LCAO
Coefficients .......................................... 154
5.4 Semiquantitative Approaches ........................... 168
5.5 Semiempirical Methods ................................. 187
5.6 Fragmentary Calculations, Molecular Mechanics, and
Combined Quantum/Classical (QM/MM) Modeling ........... 201
5.7 General Comparison of Methods ......................... 224
Summary Notes .............................................. 229
Exercises and Problems ..................................... 230
References ................................................. 231
6 Electronic Structure and Chemical Bonding .................. 238
6.1 Classification of Chemical Bonds by Electronic
Structure and Role of d and ƒ Electrons in
Coordination Bonding .................................. 238
6.2 Qualitative Aspects and Electronic Configurations ..... 246
6.3 Ligand Bonding ........................................ 254
Summary Notes .............................................. 315
Exercises and Problems ..................................... 316
References ................................................. 318
7 Electronic Control of Molecular Shapes and
Transformations via Vibronic Coupling ...................... 324
7.1 Molecular Vibrations .................................. 325
7.2 Vibronic Coupling ..................................... 337
7.3 The Jahn-Teller Effect ................................ 344
7.4 Pseudo-Jahn-Teller Effect and the Two-Level
Paradigm .............................................. 369
Summary Notes .............................................. 388
Exercises and Problems ..................................... 389
References ................................................. 390
8 Electronic Structure Investigated by Physical Methods ...... 392
8.1 Band Shapes of Electronic Spectra ..................... 393
8.2 d-d, Charge Transfer, Infrared, and Raman Spectra ..... 405
8.3 X-Ray and Ultraviolet Photoelectron Spectra; EXAFS .... 426
8.4 Magnetic Properties ................................... 443
8.5 Gamma-Resonance Spectroscopy .......................... 472
8.6 Electron Charge and Spin Density Distribution in
Diffraction Methods ................................... 483
Summary Notes .............................................. 495
Exercises and Problems ..................................... 497
References ................................................. 500
9 Stereochemistry and Crystal Chemistry ...................... 506
9.1 Definitions. Semiclassical Approaches ................. 506
9.2 Vibronic Effects in Stereochemistry ................... 519
9.3 Mutual Influence of Ligands ........................... 544
9.4 Crystal Stereochemistry ............................... 554
Summary Notes .............................................. 572
Exercises and Problems ..................................... 573
References ................................................. 575
10 Electron Transfer, Redox Properties, and Electron-
Conformational Effects ..................................... 579
10.1 Electron Transfer and Charge Transfer by
Coordination .......................................... 579
10.2 Electron Transfer in Mixed-Valence Compounds .......... 591
10.3 Electron-Conformational Effects in Biological
Systems ............................................... 609
Summary Notes .............................................. 618
Exercises and Problems ..................................... 619
References ................................................. 620
11 Reactivity and Catalytic Action ............................ 623
11.1 Electronic Factors in Reactivity ...................... 623
11.2 Electronic Control of Chemical Activation via
Vibronic Coupling ..................................... 635
11.3 Direct Computation of Energy Barriers of Chemical
Reactions ............................................. 656
Summary Notes .............................................. 686
Questions and Problems ..................................... 687
References ................................................. 689
Appendixes
Appendix 1. Tables of Characters of Irreducible
Representations of Most Usable Symmetry Point Groups
and Direct Products of Some Representations ............... 692
Appendix 2. General Expressions for the Matrix Element
Vmm of Perturbation of the States of One d Electron
in Crystal Fields of Arbitrary Symmetry .................... 697
Appendix 3. Calculation of the Destabilization and
Splitting of the States of One d Electron in Crystal
Fields of Different Symmetries ............................. 700
Appendix 4. Matrix Elements of Crystal Field Perturbation
of a Two-Electron Term F(nd)2, V'ij = 1,2,..,7
Expressed by One-Electron Matrix Elements V'mm Given
in Appendix 2 .............................................. 703
Appendix 5. Matrix Elements of Crystal Field Perturbation
of ƒ Electron States ....................................... 705
Answers and Solutions ......................................... 707
Subject Index ................................................. 745
Formula Index ................................................. 753
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